Green dye.



STATES PATENT OFFICE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISCHF- ANILIN ANDSODA FABRIK, OF LUDWIGSHAFEN, GERMANY.

GREEN DYE.

SPECIFICATION forming part of Letters Patent No. 640,986, dated January9, 1900. Application filed October 1'], 1899. Serial No. 7 33,91 7. (Nospecimens.)

To all whom it may concern;

Be it known that I, OSCAR BALLY, doctor of philosophy, a citizen of theSwiss Republic, residing at Mannheim, in the Grand Duchy of Baden andEmpire of Germany, have invented new and useful Improvements in theManufacture of Green Dye, (for which applications for patents have beenfiled in Germany, Nos. B. 24,517 and 24,518, both of April 1, 1899, andin France, Depot No. 280,790, of September 21, 1899,) of which thefollowing is a specification. I have invented a new coloring-matter ofthe anthracene series which dies unmordanted wool fast-green shades. Theinitial material for this coloring-matter is chlor-substituteddiamido-anthraquinone, such as can be obtained by treatingdiamidoanthraquinone with chlorin (either pure 1.5-diamido-anthraquinone or a crude diamido-anthraquinone, such as can beobtained byreducing the crude nitration product of anthraquinone) at theordinary temperature or at a temperature but slightly higher than theordinary temperature in the presence of a diluent, such as glacialacetic acid. This chlor-dia1nidoanthraquinone has been found to yieldvaluable coloring-matter if it be condensed with an aromatic amin andthe so-resulting condensation product be subsequently sulfonated.

In the following I will describe the manner in which my invention canbest be carried into effect. The parts are by weight,

Example 1. Production of chlor-1.5-dtamido-anthraqatnone.Ten (10) partsof 1.5-diamido-anthraquinone are suspended in two hundred (200) parts ofglacial acetic acid, and chlorin is passed into this at the ordinarytemperature or a temperature but slightly above the ordinary until theevolution of hydrochloric acid has moderated: Two reaction products willthen have been formedone in solution and the other in suspension. Thislatter is the chlor-diamidmanthraquinone, which I use as initialmaterial for my present invention. The product in suspension, which is abrick-red powder, is now filtered off. It is insoluble in cold Water,but soluble in glacial acetic acid, alcohol, nitrobenzene, and inbenzene, giving solutions Varying in color from yellowish brown to reddish brown. By crystallization from alcohol and nitro-benzene a productcan be obtained from it which crystallizes in fine brown needles,possessing the solubilities hereinbefore enumerated and which does notmelt even at 300 centigrade and whose chlorin content corresponds withthat of tetra-chlor-diamidoanthraquinone.

Example 2. Production of condensation product ofchlor-J.5-diamtdo-anthmqatnone and para-tolatdtn.Mix ten (10) parts ofthe chlor-diamido-anthraquinone obtained as directed in the precedingexample with one hundred (100) parts of para-toluidin and heat up to theboiling-point of the latter and maintain at this temperature until thecolor of the melt no longer changes. The originally-red melt becomesfinally blue green. Cool and extract with alcohol. The undissolvedresidue consists of the coloring-matter in indigolike crystals. It isdifficultly soluble in alcohol, but is more easily soluble in benzeneand in anilin, giving a blue color. Its solution in notro-benzene isgreen blue. With concentrated sulfuric acid of 66Baum it gives anolive-green color, which on heating to 100 turns violet, and if boricacid be now added the color becomes green. In this example thepara-toluidin may be substituted by para-toluidin-hydrochlorate, and adilu ent, such as naphthalene, may also be employed without materiallyaffecting the results.

Example 8. Production of a water-soluble sulfo-actd from the product ofExample 2.- Stir ten (10) parts of the product obtained according toExample 2 into one hundred (100) parts of monohydrate sulfuric acid atthe ordinary temperature. Now heat gradually to 50 centrigrade, and keepat this temperature until a test portion is completely soluble in hotwater. The new dyestuff can be isolated by pouring this melt into coldwater and salting out the sulfo-acid.

The so-obtained coloring-matter in the dry state is a green-gray powder,easily soluble in Water with a green-blue color, which water solution isscarcely affected by the addition Wool very bright fast-green shades.

IOO

Instead of para-toluidin in the above example I can also use otheraromatic amins, such as ortho-toluidin, anilin, &c. The products thenresulting can also be sulfonated according to the method given inExample 3.

The coloring-matter obtained when using chlor-substituteddiamido-anthraquinone obtained according to the method of Example 1,using, however, the crude diamido-anthraquinone, as above defined, inplace of the 1.5-diamido-anthraquinone, and subsequent treatment with anaromatic amin and subsequent sulfonation does not difier, essentially,from the products obtained according to EX- amples 1, 2, and 3.

I claim- 1. As a new article of manufacture the green coloring-matterwhich can be obtained from chlor-substituted diamido anthraquinone, ashereinbefore defined, and an aromatic amin, which in the unsulfonatedstate is insoluble in cold water, and with cold concentrated sulfuricacid gives an olive-green color, which on heating to 100 becomes violetand which violet becomes green if boric acid be added to it; in thesulfonated state it is soluble in water giving a green-blue solugreencoloring-matter which can be obtained fromchlor-1.5-diamido-anthraquinone, as hereinbefore described, andpara-toluidin, and which in the unsulfonated state is insoluble in coldwater and with cold concentrated sulfuric acid gives an olive-greencolor, which on heating to 100 becomes violet and which violet becomesgreen if boric acid be added to it; in the sulfonated state it issoluble in water giving a green-blue solution whose color is hardlyaffected by caustic soda, and gives with sulfuric acid of 66 Baum aviolet color, all substantially as hereinbefore described.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

OSCAR BALLY.

Witnesses:

ERNEST F. EI-IRHARDT, BERNHARD (J. HESSE.

